JP4502674B2 - Method for separating phosphorus-containing material from spent catalyst - Google Patents
Method for separating phosphorus-containing material from spent catalyst Download PDFInfo
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- JP4502674B2 JP4502674B2 JP2004082979A JP2004082979A JP4502674B2 JP 4502674 B2 JP4502674 B2 JP 4502674B2 JP 2004082979 A JP2004082979 A JP 2004082979A JP 2004082979 A JP2004082979 A JP 2004082979A JP 4502674 B2 JP4502674 B2 JP 4502674B2
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 63
- 239000011574 phosphorus Substances 0.000 title claims description 63
- 229910052698 phosphorus Inorganic materials 0.000 title claims description 63
- 239000003054 catalyst Substances 0.000 title claims description 36
- 238000000034 method Methods 0.000 title claims description 19
- 239000000463 material Substances 0.000 title claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 91
- 229910052759 nickel Inorganic materials 0.000 claims description 46
- 239000000047 product Substances 0.000 claims description 38
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 23
- 239000000706 filtrate Substances 0.000 claims description 23
- 229910052750 molybdenum Inorganic materials 0.000 claims description 23
- 239000011733 molybdenum Substances 0.000 claims description 23
- 229910052720 vanadium Inorganic materials 0.000 claims description 23
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 23
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 238000002386 leaching Methods 0.000 claims description 11
- 239000003208 petroleum Substances 0.000 claims description 10
- 229920002472 Starch Polymers 0.000 claims description 9
- 235000019698 starch Nutrition 0.000 claims description 9
- 239000008107 starch Substances 0.000 claims description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 6
- 150000003388 sodium compounds Chemical class 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000000926 separation method Methods 0.000 description 8
- 241000255925 Diptera Species 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910000863 Ferronickel Inorganic materials 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- -1 nickel aluminate Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Processing Of Solid Wastes (AREA)
- Removal Of Specific Substances (AREA)
- Extraction Or Liquid Replacement (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
本発明は、各種石油留分の水素化脱硫に使用された触媒からリン含有物を分離する方法に関する。 The present invention relates to a method for separating phosphorus-containing materials from a catalyst used for hydrodesulfurization of various petroleum fractions.
従来、各種石油留分の水素化脱硫触媒として、モリブデンやニッケル等が使用されている。また、水素化脱硫触媒には、使用中に石油留分に含まれていたバナジウムやニッケルが付着する。近年、水素化脱硫触媒性能を向上させるため、リンを添加する方法が用いられている。触媒の高性能化に伴い、リンを添加した触媒の量及びその添加量は増加している。 Conventionally, molybdenum, nickel, and the like have been used as hydrodesulfurization catalysts for various petroleum fractions. Further, vanadium and nickel contained in the petroleum fraction during use adhere to the hydrodesulfurization catalyst. In recent years, a method of adding phosphorus has been used in order to improve the hydrodesulfurization catalyst performance. As the performance of the catalyst increases, the amount of the catalyst to which phosphorus is added and the amount added are increasing.
触媒性能が低下して交換された使用済触媒からの、バナジウム、モリブデン、ニッケル等の有価金属の回収方法として、使用済触媒にナトリウム化合物を添加し、600℃以上の温度で焙焼して、モリブデンやバナジウムを水溶性塩にし、さらに、焙焼物を水で浸出することにより、モリブデンやバナジウムを製品化するための始液を得る方法が用いられている(例えば、特許文献1、非特許文献1及び2参照)。
上記従来方法において、使用済触媒中にリンを含有する場合、リンの大部分はニッケルと共に残渣中に留まる。このニッケル含有残渣は、フェロニッケルの原料として使用されているが、リンを含有する場合は、製品のフェロニッケル中にリンが分配するので好ましくない。 In the above conventional method, when phosphorus is contained in the spent catalyst, most of the phosphorus remains in the residue together with nickel. This nickel-containing residue is used as a raw material for ferronickel. However, when phosphorus is contained, it is not preferable because phosphorus is distributed in the ferronickel of the product.
ところで、フェロニッケル製品規格中にはリン含有量の規定があり、ニッケル含有残渣の使用量は制約を受けている。フェロニッケル原料としての使用量を増加させるには、ニッケル含有残渣中のリンを分離除去する必要がある。 By the way, in the ferronickel product specification, there is a regulation of phosphorus content, and the amount of nickel-containing residue used is restricted. In order to increase the amount used as a ferronickel raw material, it is necessary to separate and remove phosphorus in the nickel-containing residue.
本発明は、上記の実情に鑑みてなされたものであり、その目的は、使用済触媒からリン含有物を分離する方法を提供することにある。 This invention is made | formed in view of said situation, The objective is to provide the method of isolate | separating a phosphorus containing material from a used catalyst.
上記の目的を達成するため、本発明による使用済触媒からリン含有物を分離する方法は、バナジウム及びモリブデンの少なくとも一方とニッケルとリンとカルシウムを含む各種石油留分の水素化脱硫に使用されたアルミナを担体とする使用済触媒と、ナトリウム化合物を600℃以上の温度で焙焼して得られた焙焼物を、pH5以下で酸浸出し、これを濾過して、リン含有量の低いニッケル含有残渣と濾液とに分離し、更に、前記濾液をpH6から9の間に調整して、リン及びアルミニウム等を中和沈澱させ、これを濾過して、バナジウム及び/又はモリブデン製品化始液と、リン含有澱物とに分離することを特徴とする。
In order to achieve the above object, the method for separating phosphorus-containing material from the spent catalyst according to the present invention was used for hydrodesulfurization of various petroleum fractions containing at least one of vanadium and molybdenum, nickel, phosphorus and calcium . A spent catalyst using alumina as a carrier and a roasted product obtained by baking a sodium compound at a temperature of 600 ° C. or higher are acid leached at a pH of 5 or lower, filtered, and nickel-containing with a low phosphorus content The residue is separated into a filtrate, and the filtrate is further adjusted to pH 6 to 9 to neutralize and precipitate phosphorus, aluminum, etc., and filtered to obtain a vanadium and / or molybdenum product starting solution, It is characterized by separating into phosphorus-containing starch.
また、本発明による使用済触媒からリン含有物を分離する方法は、バナジウム及びモリブデンの少なくとも一方とニッケルとリンとカルシウムを含む各種石油留分の水素化脱硫に使用されたアルミナを担体とする使用済触媒と、ナトリウム化合物を600℃以上の温度で焙焼して得られた焙焼物を、pH6から9で浸出し、これを濾過して、ニッケル含有残渣とモリブデン及び/又はバナジウム製品化始液とに分離し、前記ニッケル含有残渣をpH5以下で酸浸出し、これを濾過して、リン含有量の低いニッケル含有残渣と濾液とに分離し、更に、前記濾液をpH6から9の間に調整して、リン及びアルミニウム等を中和沈澱させ、これを濾過して、バナジウム及び/又はモリブデン製品化始液と、リン含有澱物とに分離することを特徴とする。
In addition, the method for separating phosphorus-containing material from the spent catalyst according to the present invention is a method of using alumina used as a carrier for hydrodesulfurization of various petroleum fractions containing at least one of vanadium and molybdenum, nickel, phosphorus and calcium. The baked product obtained by roasting the spent catalyst and sodium compound at a temperature of 600 ° C. or higher was leached at pH 6 to 9, and filtered to obtain a nickel-containing residue and molybdenum and / or vanadium product starting solution. The nickel-containing residue is acid leached at a pH of 5 or less, filtered, and separated into a nickel-containing residue having a low phosphorus content and a filtrate, and the filtrate is adjusted to a pH between 6 and 9. And neutralizing and precipitating phosphorus, aluminum, etc., and filtering this to separate into vanadium and / or molybdenum product starting solution and phosphorus-containing starch.
また、本発明による使用済触媒からリン含有物を分離する方法は、バナジウム及びモリブデンの少なくとも一方とニッケルとリンとカルシウムを含む各種石油留分の水素化脱硫に使用されたアルミナを担体とする使用済触媒と、ナトリウム化合物を600℃以上の温度で焙焼して得られた焙焼物を、pH10以上でアルカリ浸出し、これを濾過して、ニッケル含有残渣と濾液とに分離し、更に、前記ニッケル含有残渣をpH5以下で酸浸出し、これを濾過して、リン含有量の低いニッケル含有残渣と濾液とに分離し、前記各濾液をpH6から9に調整して、リン及びアルミニウム等を中和沈澱させ、これを濾過して、モリブデン及び/又はバナジウム製品化始液と、リン含有澱物とに分離することを特徴とする。
In addition, the method for separating phosphorus-containing material from the spent catalyst according to the present invention is a method of using alumina used as a carrier for hydrodesulfurization of various petroleum fractions containing at least one of vanadium and molybdenum, nickel, phosphorus and calcium. The baked product obtained by roasting the spent catalyst and the sodium compound at a temperature of 600 ° C. or higher is alkali leached at a pH of 10 or higher, filtered, and separated into a nickel-containing residue and a filtrate. The nickel-containing residue is acid leached at a pH of 5 or less, filtered, and separated into a nickel-containing residue and a filtrate having a low phosphorus content. The filtrates are adjusted to pH 6 to 9, and phosphorus, aluminum, and the like are contained therein. It is characterized in that it is precipitated and filtered to separate into molybdenum and / or vanadium product starting liquid and phosphorus-containing starch.
本発明によれば、使用済触媒から効率良くリン含有物を分離することができ、延いては、リン含有量の低いフェロニッケル原料等を提供することができる。 According to the present invention, it is possible to efficiently separate a phosphorus-containing material from a used catalyst, and thus it is possible to provide a ferronickel raw material having a low phosphorus content.
本第1の発明によるニッケル含有残渣中のリンの分離除去は、図1に示す通り、バナジウム及びモリブデンの少なくとも一方とニッケルとリンとカルシウムを含む各種石油留分の水素化脱硫に使用されたアルミナを担体とする使用済触媒と、ナトリウム化合物を600℃以上の温度で焙焼して得られた焙焼物を、pH5以下で酸浸出し、これを濾過して、リン含有量の低いニッケル含有残渣と濾液とに分離し、更に、前記濾液をpH6から9の間に調整して、これを濾過して、リン及びアルミニウム及びリン含有澱物と、バナジウム及び/又はモリブデン製品化始液に分離することにより行なわれる。
As shown in FIG. 1, the separation and removal of phosphorus in the nickel-containing residue according to the first aspect of the present invention is the use of alumina used for hydrodesulfurization of various petroleum fractions containing at least one of vanadium and molybdenum, nickel, phosphorus and calcium. A nickel-containing residue having a low phosphorus content is obtained by acid leaching a spent catalyst obtained by using a catalyst as a carrier and a roasted product obtained by baking a sodium compound at a temperature of 600 ° C. or higher at pH 5 or lower, and filtering this. In addition, the filtrate is adjusted to pH 6-9 and filtered to separate phosphorus and aluminum and phosphorus-containing starch and vanadium and / or molybdenum product starting solution. Is done.
水素化脱硫触媒の担体はアルミナである。一方、使用済触媒中のニッケルは、硫化物もしくは酸化物として存在している。焙焼により、ニッケル硫化物は酸化されて酸化物となる。ニッケル酸化物とアルミナは、反応してニッケルアルミネートとなる。また、アルミナの大部分は、アルファ・アルミナとなり、ニッケル及びアルミニウムは、浸出し難い化合物形態となる。一方、リンの大部分は、リン酸ナトリウム、リン酸アルミニウム、リン酸カルシウム等の形態で焙焼物中に存在する。 The support for the hydrodesulfurization catalyst is alumina. On the other hand, nickel in the used catalyst exists as sulfide or oxide. By roasting, the nickel sulfide is oxidized to an oxide. Nickel oxide and alumina react to form nickel aluminate. Further, most of alumina becomes alpha-alumina, and nickel and aluminum are in a compound form that hardly leaches. On the other hand, most of phosphorus is present in the roasted product in the form of sodium phosphate, aluminum phosphate, calcium phosphate or the like.
カルシウムの含有量に差のある2種類の使用済触媒に炭酸ナトリウムを加え、900℃で焙焼した焙焼物のICP分析値を下表1に示す。使用済触媒中にカルシウムが含まれている場合は、pH5以下で酸浸出するのが効果的である。これにより、リン酸カルシウムも浸出することができる。一方、使用済触媒中のカルシウムが少ない場合は、アルミニウムやニッケルの浸出量の減少するpH10以上で浸出するのが効果的である。
Table 1 below shows ICP analysis values of the baked product obtained by adding sodium carbonate to two kinds of used catalysts having different calcium contents and baking at 900 ° C. If it contains spent catalyst mosquito Le Siumu in, it is effective to acid leaching at pH5 or less. Thus, it is possible to leach phosphorylation Le Siumu. On the other hand, if the mosquito Le Siumu in the spent catalyst is small, leaching of aluminum and nickel leaching of decreasing pH10 or more is effective.
表1
Table 1
また、本第2の発明によるニッケル含有残渣中のリンの分離除去は、図2に示す通り、上記焙焼物をpH6から9で浸出し、これを濾過して、ニッケル含有残渣とモリブデン及び/又はバナジウム製品化始液とに分離し、このニッケル含有残渣をpH5以下で酸浸出し、リン含有量の低いニッケル含有残渣と濾液とに分離し、更に、この濾液をpH6から9の間に調整して、濾過し、リン及びアルミニウム含有澱物と、バナジウム及び/又はモリブデン製品化始液とに分離することにより行なわれる。
Further, the separation and removal of phosphorus in the nickel-containing residue according to the second aspect of the present invention is carried out by leaching the roasted product at pH 6 to 9 and filtering it, as shown in FIG. The nickel-containing residue is acid leached at a pH of 5 or less, separated into a nickel-containing residue having a low phosphorus content and a filtrate, and the filtrate is adjusted to a pH between 6 and 9. Filtration and separation into phosphorus and aluminum containing starch and vanadium and / or molybdenum product starting liquor.
この場合、濾液へのリンやアルミニウム浸出量は少なく、濾液をモリブデン、バナジウム製品化始液とすることができる。一方、ニッケル含有残渣中のリンを分離除去しなければならない。上記と同様、使用済触媒中にカルシウムが含まれている場合は、pH5以下で酸浸出するのが効果的であり、使用済触媒中のカルシウムが少ない場合は、pH10以上で浸出するのが効果的である。
In this case, the amount of leaching of phosphorus and aluminum into the filtrate is small, and the filtrate can be used as a molybdenum or vanadium product starting solution. On the other hand, the phosphorus in the nickel-containing residue must be separated and removed. As described above, if it contains a mosquito Le Siumu in the spent catalyst is effective is to acid leaching at pH5 or less, when mosquito Le Siumu in the spent catalyst is small, leaching at pH10 or It is effective to do.
さらに、本第3の発明によるニッケル含有残渣中のリンの分離除去は、図3に示す通り、上記焙焼物をpH10以上でアルカリ浸出し、濾過し、ニッケル含有残渣と濾液とに分離し、更に、ニッケル含有残渣をpH5以下で酸浸出し、濾過し、リン含有量の低いニッケル含有残渣と濾液とに分離し、前記各濾液をpH6から9に調整して、濾過し、アルミニウム及びリン含有澱物とモリブデン、バナジウム製品化始液とに分離することにより行なわれる。
Further, the separation and removal of phosphorus in the nickel-containing residue according to the third aspect of the invention, as shown in FIG. 3, the baked product is alkali-leached at a pH of 10 or more, filtered, and separated into a nickel-containing residue and a filtrate. The nickel-containing residue is acid leached at a pH of 5 or less, filtered, and separated into a nickel-containing residue and a filtrate having a low phosphorus content, and each filtrate is adjusted to a pH of 6 to 9 and filtered to obtain an aluminum and phosphorus-containing starch. By separating the product into molybdenum and vanadium product starting solution.
この場合も、得れた焙焼物をpH5以下で酸浸出し、濾過し、ニッケル含有残渣と濾液とに分離する。ニッケル含有残渣を、更にpH10以上でアルカリ浸出する。また、最初にpH10以上でアルカリ浸出したニッケル含有残渣を、更にpH5以下で酸浸出しても、同様にリン含有量の低いニッケル含有残渣を得ることができる。 Also in this case, the obtained roasted product is acid leached at pH 5 or less, filtered, and separated into a nickel-containing residue and a filtrate. The nickel-containing residue is further alkaline leached at a pH of 10 or higher. Further, even when the nickel-containing residue initially leached with alkali at pH 10 or higher is further acid leached at pH 5 or lower, a nickel-containing residue having a low phosphorus content can be obtained.
以下、本発明の実施例を説明する。
上記表1の焙焼物A、B各々30gをイオン交換水150mlに浸し、水酸化ナトリウム溶液でpH8.0に調整しながら50℃で60分浸出し、5C濾紙で濾過した。更に、得られた残渣をイオン交換水50mlで洗浄濾過し、ICP分析した。以上の結果を、下表2に示す。残渣には、リンが焙焼物Aで0.72乾燥重量%、焙焼物Bで0.69乾燥重量%残留した。
Examples of the present invention will be described below.
30 g of each of the baked products A and B shown in Table 1 above were immersed in 150 ml of ion-exchanged water, leached at 50 ° C. for 60 minutes while adjusting to pH 8.0 with a sodium hydroxide solution, and filtered through 5C filter paper. Further, the obtained residue was washed and filtered with 50 ml of ion-exchanged water and analyzed by ICP. The above results are shown in Table 2 below. In the residue, 0.72% by weight of phosphorus remained in the roasted product A and 0.69% by dry weight of the roasted product B remained in the residue.
表2
Table 2
実施例1
表1の焙焼物A、B各々30gをイオン交換水150mlに浸し、水酸化ナトリウム溶液でpH12.0に調整しながら50℃で60分浸出し、5C濾紙で濾過した。更に、得られた残渣をイオン交換水50mlで洗浄濾過し、ICP分析した。同様に、イオン交換水150mlに浸し、硫酸溶液でpH1.5に調整しながら浸出した。以上の結果が表2に示されている。焙焼物Aの場合、pH12.0よりpH1.5の方がリンの除去分離効果が大きい。
一方、カルシウムの少ない焙焼物Bにおいては、pH12.0とpH1.5に差はなかった。
Example 1
30 g of each of the baked products A and B shown in Table 1 were immersed in 150 ml of ion-exchanged water, leached at 50 ° C. for 60 minutes while adjusting to pH 12.0 with a sodium hydroxide solution, and filtered through 5C filter paper. Further, the obtained residue was washed and filtered with 50 ml of ion-exchanged water and analyzed by ICP. Similarly, it was immersed in 150 ml of ion exchange water and leached while adjusting to pH 1.5 with a sulfuric acid solution. The above results are shown in Table 2. In the case of the baked product A, the removal and separation effect of phosphorus is greater at pH 1.5 than at pH 12.0.
On the other hand, in the small roasting product B of mosquitoes Le Siumu was no difference pH12.0 and pH 1.5.
実施例2
表1の焙焼物A、B各々30gをイオン交換水150mlに浸し、水酸化ナトリウム溶液でpH8.0に調整しながら50℃で60分浸出し、5C濾紙で濾過した。更に、残渣をイオン交換水50mlで洗浄濾過し、残渣を得た。この残渣をイオン交換水150mlに浸し、水酸化ナトリウム溶液でpH12.0に調整しながら50℃で60分浸出し、5C濾紙で濾過した。更に、残渣をイオン交換水50mlで洗浄濾過し、ICP分析した。同様に、pH8.0の浸出残渣をイオン交換水150mlに浸し、硫酸溶液でpH1.5に調整しながら浸出した。以上の結果が表2に示されている。焙焼物Aの場合、pH12.0よりpH1.5の方がリンの除去分離効果が大きい。
一方、カルシウムの少ない焙焼物Bにおいては、pH12.0とpH1.5に差はなかった。
Example 2
30 g of each of the baked products A and B shown in Table 1 were immersed in 150 ml of ion-exchanged water, leached for 60 minutes at 50 ° C. while adjusting to pH 8.0 with a sodium hydroxide solution, and filtered through 5C filter paper. Furthermore, the residue was washed and filtered with 50 ml of ion exchange water to obtain a residue. This residue was immersed in 150 ml of ion-exchanged water, leached for 60 minutes at 50 ° C. while adjusting the pH to 12.0 with a sodium hydroxide solution, and filtered through 5C filter paper. Further, the residue was washed and filtered with 50 ml of ion-exchanged water and analyzed by ICP. Similarly, the leaching residue of pH 8.0 was immersed in 150 ml of ion exchange water and leached while adjusting to pH 1.5 with a sulfuric acid solution. The above results are shown in Table 2. In the case of the roasted product A, the removal and separation effect of phosphorus is larger at pH 1.5 than at pH 12.0.
On the other hand, in the small roasting product B of mosquitoes Le Siumu was no difference pH12.0 and pH 1.5.
実施例3
表1の焙焼物A、B各々30gをイオン交換水150mlに浸し、水酸化ナトリウム溶液でpH12.0に調整しながら50℃で60分浸出し、5C濾紙で濾過し、更に、残渣をイオン交換水50mlで洗浄濾過し、残渣を得た。この残渣をイオン交換水150mlに浸し、硫酸溶液でpH1.5に調整しながら浸出し、5C濾紙で濾過し、更に残渣をイオン交換水50mlで洗浄濾過し、得られた残渣をICP分析した。同様に、上記のpHを1.5、2.0として実施した。以上の結果が表2に示されている。焙焼物A及びBともに、リンの除去分離に差はなかった。また、最もリン含有量の低いニッケル残渣が得られた。
Example 3
30 g of each of the baked products A and B in Table 1 are immersed in 150 ml of ion exchange water, adjusted to pH 12.0 with a sodium hydroxide solution, leached for 60 minutes at 50 ° C., filtered through 5C filter paper, and the residue is ion exchanged. Washing and filtration with 50 ml of water gave a residue. The residue was immersed in 150 ml of ion-exchanged water, leached while adjusting to pH 1.5 with a sulfuric acid solution, filtered through 5C filter paper, the residue was further washed and filtered with 50 ml of ion-exchanged water, and the obtained residue was analyzed by ICP. Similarly, the above pH was set to 1.5 and 2.0. The above results are shown in Table 2. There was no difference in the removal and separation of phosphorus in the baked products A and B. Moreover, the nickel residue with the lowest phosphorus content was obtained.
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US7741239B2 (en) * | 2008-03-11 | 2010-06-22 | Evonik Energy Services Llc | Methods of regeneration of SCR catalyst poisoned by phosphorous components in flue gas |
CN102219258A (en) * | 2010-04-14 | 2011-10-19 | 湖南荣宏钼业材料股份有限公司 | Method for extracting molybdenum from waste materials in ammonium molybdate production field |
JP5691732B2 (en) * | 2011-03-29 | 2015-04-01 | 住友金属鉱山株式会社 | Method for producing molybdenum trioxide |
JP5810897B2 (en) * | 2011-12-26 | 2015-11-11 | 住友金属鉱山株式会社 | Process of leachate |
FI127859B (en) * | 2014-03-31 | 2019-04-15 | Upm Kymmene Corp | Method and system for reducing phosphorus in effluent or filtrate |
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JPS51125617A (en) * | 1974-12-19 | 1976-11-02 | Akzo Nv | Metal leaching from waste desulphrizing catalyser |
JPS52155102A (en) * | 1976-06-18 | 1977-12-23 | Taiwa Kk | Process for recovery of valuable metal from spent catalyst |
JPH05156375A (en) * | 1991-12-05 | 1993-06-22 | Taiyo Koukou Kk | Method for leaching valuable metal from waste catalyst |
JPH0657353A (en) * | 1992-02-07 | 1994-03-01 | Eurecat Europ De Retraitement De Catalyseurs | Recovery of molybdenum and vanadium from used catalyst |
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JPS52155102A (en) * | 1976-06-18 | 1977-12-23 | Taiwa Kk | Process for recovery of valuable metal from spent catalyst |
JPH05156375A (en) * | 1991-12-05 | 1993-06-22 | Taiyo Koukou Kk | Method for leaching valuable metal from waste catalyst |
JPH0657353A (en) * | 1992-02-07 | 1994-03-01 | Eurecat Europ De Retraitement De Catalyseurs | Recovery of molybdenum and vanadium from used catalyst |
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